减压蒸馏生物油与乙醇在ZSM-5/MCM-41上共催化裂化

采用减压蒸馏生物油为原料,与无水乙醇2:3(质量比)混合,在固定床中ZSM-5/MCM-41分子筛上共催化裂化,考查了反应温度和质量空速(WHSV)对裂化产物的影响。对ZSM-5/MCM-41进行了NH₃-TPD、BET、N₂吸附-脱附等表征,对裂化气体产物通过气相色谱仪分析,减压蒸馏生物油和精制生物油采用气相色谱-质谱联用仪进行定量分析。结果表明,反应温度500 ℃、WHSV 3.75 h^-1为反应优化工况。此反应条件下,精制生物油酸类物质从减压蒸馏生物油中的25.6%降至反应后的0.1%,效果显著,且精制生物油产率为46.8%,气体产物中CO₂和CO的浓度共9.5%。     

电催化氧化制备2,5-呋喃二甲酸

在第75届联合国大会上,我国承诺力争在2030年前实现碳达峰、2060年前实现碳中和。主要由光合作用产生的生物质将在双碳目标中扮演重要角色,通过高效转化可衍生出一系列替代化石产品的高值化学品。其中,2,5-呋喃二甲酸(FDCA)由于具有与石油基对苯二甲酸(TPA)相似的共轭碳环和二酸结构,可替代TPA用于合成热稳定性能、气体阻隔性能更优的生物基呋喃聚酯,大幅降低聚酯行业对化石资源的严重依赖。此外,FDCA在医药、香料、金属配位化学方面也有广泛应用,从而被认为是12种最具潜力的生物基平台化合物之一。FDCA通常可由5-羟甲基糠醛(HMF)通过催化氧化进行合成。相比于需要贵金属催化剂、高温和高压条件、以化学势作为驱动力的传统热催化方法,电催化氧化采用电极电势作为主要驱动力,是更为绿色和高效的新颖合成方法。本综述对电催化氧化制备FDCA反应所用的贵金属、过渡金属和非金属催化剂进行了总结与分析,梳理了催化剂设计和反应机理的研究脉络,并指出了该领域发展所面临的挑战与机遇。     

HZSM-5催化剂上超临界乙醇中生物油催化提质及检测方法研究

采用不同硅铝比的HZSM-5催化剂,在不同条件下(超临界、亚超临界、非超临界乙醇)催化提质生物油中的高沸点组分(HBF),应用磷核磁共振(31P-NMR)定量检测了提质前后生物油中醇、酚和羧酸类羟基的质量比(羟基质量/生物油质量)变化,研究和评价了催化剂和超临界条件对生物油催化提质的效果.研究表明,超临界条件有利于生物油中脂肪族羟基的转化,但是不利于非缩合羟基的转化;使用不同酸强度的HZSM-5都能使生物油中的羧基完全转化,增加催化剂的酸强度可以促进脂肪族羟基的转化,而只有酸性较弱的催化剂才能顺利转化非缩合酚羟基.     

基于原理实例检索的可变功能产品功能升级再设计

针对可变功能产品随市场变化导致其功能和性能存在不足之处的情况, 提出了用于该类产品功能升级再设计的“原理实例检索法”. 首先, 归纳总结出功能升级的4种基本类型, 依据总结出的功能升级类型, 从功能需求的角度出发, 提出了一个功能升级辅助再设计软件原型系统, 用以进行原理实例的检索. 若检索结果无相关原理或实例支持功能升级, 则对升级功能进行TRIZ(发明问题解决理论)工程参数转化, 通过构建冲突矩阵获得创新原理解. 以电动工具为例, 建立的功能升级辅助再设计系统搜集了用于实现电动工具常见功能的基本原理和实例, 并利用Access数据库和Visual Basic 6.0对设计信息进行存储和原型系统构建. 其次, 对升级功能结构和原共享结构间的匹配情况进行分析, 得出结构匹配可能出现的5类基本情况. 最后, 以电钻“打磨固体”升级功能设计为实例, 利用上述功能升级再设计方法, 设计出了磨砺性能良好的“去锈打磨盘”, 验证了所提出的可变功能产品功能升级再设计方法的可行性.     

Aqueous-phase catalytic hydrogenation of furfural to cyclopentanol over Cu-Mg-Al hydrotalcites derived catalysts: Model reaction for upgrading of bio-oil

A series of Cu-Mg-Al hydrotalcites derived oxides with a (Cu+Mg)/Al mole ratio of 3 and varied Cu/Mg mole ratio (from 0.07 to 0.30) were prepared by co-precipitation and calcination methods, then they were introduced to the hydrogenation of furfural in aqueous-phase. Effects of Cu/Mg mole ratio, reaction temperature, initial hydrogen pressure, reaction time and catalyst amount on the conversion rate of furfural as well as the selectivity toward desired product cyclopentanol were systematically investigated. The conversion of furfural over calcined hydrotalcite catalyst with a Cu/Mg mole ratio of 0.2 was up to 98.5% when the reaction was carried out under 140 °C and the initial hydrogen pressure of 4 MPa for 10 h, while the selectivity toward cyclopentanol was up to 94.8%. The catalysts were characterized by XRD and SEM. XRD diffraction of all the samples showed characteristic pattern of hydrotalcite with varied peak intensity as a result of different Cu content. The catalytic activity was improved gradually with the increase of Cu component in the hydrotalcite.     

Fungal upgrading of wheat straw for straw-thermoplastics production

Combining biologic pretreatment with storage is an innovative approach for improving feedstock characteristics and cost, but the magnitude of responses of such systems to upsets is unknown. Unsterile wheat straw stems were upgraded for 12 wk with Pleurotus ostreatus at constant temperature to estimate the variation in final compositions with variations in initial moisture and inoculum. Degradation rates and conversions increased with both moisture and inoculum. A regression analysis indicated that system performance was quite stable with respect to inoculum and moisture content after 6 wk of treatment. Scale-up by 150× indicated that system stability and final straw composition are sensitive to inoculum source, history, and inoculation method. Comparative testing of straw-thermoplastic composites produced from upgraded stems is under way.     

超临界水中煤焦油沥青轻质化的实验研究

采用间歇超临界水（supercritical water, SCW）反应器,考察了反应温度（400℃~480℃）、停留时间(1 min~80 min)和反应压力（25 MPa~40 MPa）对煤焦油沥青轻质化的影响。与常压N2热解相比,煤焦油沥青在SCW中反应后产物中的轻油质量分数高,残焦质量分数低,表明SCW可以促进煤焦油沥青的轻质化反应进行并抑制缩合反应。沥青质是煤焦油沥青在SCW中发生反应的主要组分。在440 ℃和34 MPa时反应20 min,产物中轻油的质量分数可达原料的两倍,说明煤焦油沥青在SCW中可以发生明显轻质化反应。与温度相比,压力和停留时间的影响相对较小。     

Selective Production of Carbon Monoxide via Methane Oxychlorination over Vanadyl Pyrophosphate

A catalytic process is demonstrated for the selective conversion of methane into carbon monoxide via oxychlorination chemistry. The process involves addition of HCl to a CH₄–O₂ feed to facilitate C?H bond activation under mild conditions, leading to the formation of chloromethanes, CH₃Cl and CH₂Cl₂. The latter are oxidized in situ over the same catalyst, yielding CO and recycling HCl. A material exhibiting chlorine evolution by HCl oxidation, high activity to oxidize chloromethanes into CO, and no ability to oxidize CO, is therefore essential to accomplish this target. Following these design criteria, vanadyl pyrophosphate (VPO) was identified as an outstanding catalyst, exhibiting a CO yield up to approximately 35 % at 96 % selectivity and stable behavior. These findings constitute a basis for the development of a process enabling the on‐site valorization of stranded natural‐gas reserves using CO as a highly versatile platform molecule.     

Chromatographic characterization of thermally upgraded products from alternative fuels

An overview is presented of the analytical approaches developed by our research group over the last ten years for analysis of alternative fuel, both biomass and fossil. The alternative fuels are analyzed successively by PLC-8 (preparative liquid chromatography–group-type) fractionation and high resolution gas chromatography. Some of the possibilities for fractionation and characterization of alternative fuels are herein exemplified with sugar cane bagasse pyrolysis products.